CH653019A5 - N-BETA AMINOAETHYL PIPERIDINE COMPOUNDS. - Google Patents

Description

The present invention relates to N-β-aminoethylpiperidine compounds of the formula I, their preparation and their use as stabilizers against degradation by light and in particular heat of polymeric organic materials. Compounds of the formula

%H_

N - CH ~ - Gi "

- y— OR ^ (I) /

h3c ch3

condensed,

are those in which

Ri is hydrogen, or a radical O

20 «

- c - x - r,

(a)

wherein the two R5 have the meanings given in claim 1.

5. A method for stabilizing plastics against degradation by light, characterized in that the plastics to be stabilized have at least one compound of the formula I, according to claim 1, in amounts of 0.01 to 5%, based on the total weight, during or after polymer formation, adds to the mass.

6. The method according to claim 5, characterized in that plastics are stabilized in the form of industrial paintwork, preferably stove enamels, in particular vehicle paints.

7. Stabilized plastics which contain from 0.01 to 5% by weight of at least one compound of the formula I as a light stabilizer, prepared by the process according to claim 5.

8. Stabilized plastics according to claim 7, produced by the process according to claim 6, in the form of industrial coatings, preferably stove enamels, in particular vehicle coatings.

9. Light stabilizers, in the form of a concentrate, which contain at least one compound of formula I, according to claim 1, in an amount of 20 to 80 wt .-%.

X is the direct bond, oxygen or NH, R2 is hydrogen or alky ^ Cj. , 8) or a radical (a), 25 R3 hydrogen, alkyl (C, _ | S) or one of the radicals (b), (c) or (d):

r-

+ ai2 ^ N - a, 2 - ®2 - n

35

H3C GÎ3

(b),

where m 2-10,

Ce),

R'z is hydrogen or alkyl (C, _18), where if R3 is an (gl-,) -c nen of the radicals (c) or (d): R2 = R'2, 60 \.

R2 and R3 together with the N atom to which they are attached (~ y) (QI (e)

are bound, a succinimide, maleimide or phthali- y —- y 2 11

midring,

R4 alkyl (CMg) for X = NH optionally by 65 3 ^

-N = C = O is substituted, cycloalkyI (C5 g), phenylal-

kyl (C1_4), optionally with 1 or 2 alkyl (C, _I2) with zero, 1 or 2,

a maximum of 18 C atoms are substituted phenyl, or R5 is independently chlorine,

653 019

4th

- n

A *

(f),

%

o3sr - N - Œ2- CH2 - N

R6 is alkylene (C210) or phenylene which is optionally substituted by alkyl (C (_9) and for X = direct bond R6 is also -CH2- or the direct bond,

R7 hydrogen, alkyl (CM8), ß-hydroxyethyl,

R8 alkyl (CMg), ß-hydroxyethyl or phenyl, or

R7 and R8 together with the N atom to which they are attached represent a residue of the piperidine or morpholine.

In the above formulas, Rls preferably means R \, i.e. Hydrogen or a radical (a), in which X is NH or the direct bond, preferably hydrogen. X preferably denotes the direct bond or NH, preferably the direct bond.

R2 preferably denotes R'2, preferably hydrogen and in the event that R3 = hydrogen: preferably a radical (a). If a radical (c) or (d) is present, all substituents R2 have one of the meanings of R'2. R'2 as alkyl is preferably alkyl (CW2). m is preferably 8 or 10.

R3 is preferably R'3, i.e. Alkyl (C, _, 8) or one of the radicals (c) or (d), preferably R "3, i.e. a radical (c).

Means R! is a radical (a), R3 is preferably hydrogen and R2 is preferably also a radical (a) or R2 and R3 together with the common N atom is a succinimide, maleimide or phthalimide ring. Preferably R ,, have the same meaning in the event that R, = (a), and R2.

R + is preferably alkyl (CM8), cyclohexyl, benzyl or phenyl, preferably alkyl (CM8). R3 and R4 as alkyl preferably have 8-18 C atoms.

n is preferably zero or 2, preferably 2.

In the rest (c) it preferably has 1 or 2 further radicals

(G)-

The remainder (0 preferably denotes a piperidinyl or morpholinyl ring.

R6 for X = the direct bond preferably means alkylene (C + s) or p-phenylene. Rö for X = NH preferably means alkylene (C4 12) or phenylene optionally substituted by 1 or 2 alkyl (C, 4), preferably hexamethylene.

R, together with R8, preferably denotes a pipe-ridinyl or morpholinyl ring.

Compounds of the formulas are preferred

H

3 ^ 3

r4-x - c - hn-ch2-ch2- ^ _y ~ or £

h3c ch3

R ^ HN - Œ2

(Ib)

H3C Œ3

(9),

io Of the compounds of formula (Ia) are those of the formula

15

25th

0 ¥ ^ 3 0

R'4 -C- NH - CH2 - CH2 - N ^) - 0 - C - R'4

V CH3 (laa),

prefers.

The preparation of the compounds of the formula I is characterized in that one mole of a compound of the formula

H3 ^ 3

h2m-œ2-ct2-n ^ y— ce Ol)

30th

h3c ch3

the reduction product of a compound of the formula III 35 or IV (see below),

for R2 and / or R3 = alkyl: reacted in a manner known per se with 1 or 2 mol of an alkylating agent,

40

for R, and / or R2 O

O

I-

R4: with 1 or 2 moles of one

Compound R4-C-0H or a suitable functional

45 len derivative thereof, acylated,

O

- for R! and / or R2 = -C-O-r4 .: with 1 or 2 moles of one

50 compound R40-C acylated,

^ C1

O

for Rt and / or R, = -C-NH-r4 .: acylated with 1 or 2 mol of a compound of the formula R4-N = C = O,

55 - for R3 = a radical (b): acylated with half a mole of a compound of the formula HOOC- (CH2) m-, COOH, or a functional derivative thereof, in which m 'is zero or 1-8, and then the product hydrated,

60 - for R3 = a radical (d), where X = the direct bond: with half a mole of a compound of the formula

O

O

II

(la).

ho-c-r6-c-oh or a functional derivative thereof, acylated, for R3 = a radical (d), where X = oxygen: with half a mo} of a compound of the formula

5

653 019

Il sS ™

ci-c-o-r6-o-c acylated,

for R3 = a radical (d), in which X = NH: acylated with half a mole of a compound of the formula O = C = N-R6 - N = C = O,

- for R3 = (c): with 1 mol of a compound of the formula

Cl

■ Â

where A is independently chlorine, a radical (f) or (g), condenses - for R2 and R3 together with the common N atom, a succinimide, maleimide or phthalimide ring: with 1 mol succinic anhydride, maleic anhydride or phthalic anhydride implemented in a manner known per se.

The process for the preparation of the compound of the formula II is characterized in that a compound of the formula nc - ct2

^ "^ 2 W -

h3c œ3

reduced in a conventional manner.

The process for the preparation of the compound of formula III is characterized in that triacetonamine is preferably reacted in an aqueous solution with glycolonitrile in a manner known per se. The process for the preparation of the compound of formula IV is characterized in that 4-hydroxy-2,2,6,6-tetramethylpiperidine, with glycolonitrile, preferably in aqueous solution, is reacted in a manner known per se.

Instead of glycolic acid nitrile, a mixture of acetone cyanohydrin and formaldehyde is preferably used.

The present invention also relates to a process for stabilizing plastics against degradation by light, characterized in that the plastics to be stabilized are given a compound of the formula I in a concentration of 0.01 to 5% by weight. preferably 0.02 to 1 wt .-% before, during or after the polymer formation.

The invention also relates to stabilized plastics which contain 0.01-5% by weight, preferably 0.02-1% by weight, of a compound of the formula I as light stabilizers, and agents, for. B. so-called. Masterbatches or liquid concentrates which contain a compound of formula I in a concentration of 20-80 wt .-%, preferably 40-60 wt .-%.

The compounds of the formula I can be used above all as light stabilizers.

The application possibilities 5 in the plastics sector are particularly numerous. For example, for polyolefins, especially polyethylene and polypropylene, ethylene / propyl-encopolymer, polybutylene, as well as polystyrene, chlorinated polyethylene, and also polyvinyl chloride, polyester, polycarbonate, polymethyl methacrylates, polyphenylene oxides, polyamides such as io nylon, polyurethanes, polypropylene oxide, polyacetals, phenol-formaldehyde resins, Epoxy resins, polyacrylonitrile and corresponding copolymers as well as ABS terpolymers. The compounds according to the invention are preferably used to stabilize polypropylene, polyethylene i5, including high molecular weight polyethylene, ethylene / propylene copolymers, polyvinyl chloride, polyester, polyamide, polyurethanes, polyacrylonitrile, ABS terpolymers, terpolymers of acrylic esters, styrene and acrylonitrile, copolymers of styrene and acrylonitrile or styrene and butadiene, preferably for polypropylene, polyethylene, ethylene / propylene copolymer or ABS.

Natural substances can also be stabilized, such as rubber and also lubricating oils. The incorporation or coating of the materials 25 to be protected takes place according to methods known per se. A particularly important application method is the intimate mixing of a plastic with the new compounds in the melt e.g. in a kneader or by extrusion, injection molding, blow molding, spinning to the corresponding 30 items. Polypropylene or polyethylene in granular, semolina or powder form is preferably used.

When processing z. B. by extrusion, injection molding, Ro-tationsguss or blow molding, for example, films, films, hoses, tubes, containers, bottles, 35-profile parts, threads or tapes or foams. You can also coat metal wires with the polymer melt using a suitable extruder.

The plastics do not necessarily have to be completely polymerized or condensed before they are mixed with the 40 compounds according to the invention. It is also possible to mix monomers or prepolymers or precondensates with the stabilizers according to the invention and only afterwards to convert the plastic into the final form during or after the condensation or polymerization. 45 In addition to the compounds of formula (I), other stabilizers can also be added to the plastics. Such further connections are e.g. B. antioxidants based on sterically hindered phenols or sulfur- or phosphorus-containing costabilizers or a mixture of suitable sterically hindered phenols and sulfur and / or phosphorus-containing compounds. Such connections are e.g. Benzofuranone (2) and / or indolinone (2) compounds, sterically hindered phenols such as ß- (4-hydroxy-3,5-di-tert.-butylphenyl) propionic acid stearyl 55 ester,

Tetrakis [methylene-3 (3 ', 5'-di-tert-butyl-4-hydroxyphenyl -) propionate] methane,

1.3.3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane,

1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -l, 3.5-60 triazine-2,4,6 (1H, 3H, 5H) -trione, Bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiolte-rephthalate,

Tris- (3,5-ditert.-butyl-4-hydroxy-benzyl) -isocyanurate, triester of ß- (4-hydroxy-3,5-ditertbutyl-phenyl) propion-65 acid with

1.3.4-tris- (2-hydroxyethyl) -5-triazine-2,4,6 (1H, 3H, 5H) -trione, bis- [3,3-bis- (4'-hydroxy-3-tert. -butylphenyl) -butanoic acid] -

glycolester.

H3y®3

- n W> (HI) or

CH3 H3yCH3

- TsT 3 TO (T \ T \

653 019

6

1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxy-

benzyl-) benzene, 2,2'-methylene-bis- (4-methyl-6-tert-butylphenyl) terephthalate

lat,

4,4-methylene-bis- (2,6-di-tert-butylphenol, 4,4'-butylidene-bis - (- tert-butyl-meta-cresol), 4,4-thio-bis- (2- tert-butyl-5-methyl-phenol), 2,2'-methylene-bis- (4-methyl-6-tert-butyl-phenol).

Antioxidant co-stabilizers can also be added, such as. B. sulfur-containing compounds, e.g.

Distearyl thiodipropionate,

Dilauryl thiodipropionate,

Tetrakis (methylene-3-hexyl-thiopropionate) methane, tetrakis (methylene-3-dodecyl-thiopropionate) methane and dioctadecyl disulfide or phosphorus-containing compounds such as e.g. Trinonylphenyl phosphite;

4,9-distearyl-3,5,8,10-tetraoxadiphosphaspiroundecane, tris (2,4-ditert.-butylphenyl) phosphite or tetrakis (2,4-ditert.-butylphenyl) -4,4'-biphenylylene -diphosphonite.

The compounds according to the invention and their mixtures mentioned above can also be used in the presence of further additives. Such are known per se and e.g. described in DOS 2 606 358. These include e.g. to the group of aminoaryl compounds, UV absorbers and light stabilizers such as the 2- (2'hydroxyphenyl) benzotriazoles, 2-hydroxybenzophenones, 1,3-bis (2'hydroxybenzolylbenzenes, salicylates, cinnamic acid esters, esters of optionally substituted benzoic acids, sterically hindered amines, oxalic acid diamides.

Other additives are e.g. B. flame retardant, antistatic ka and other known additives.

The compounds of the formula I are eminently suitable for use in stove enamels, in particular vehicle finishes, especially two-coat finishes such as B. Metallisé paintwork for automobiles. Such paints, in particular car paints, which contain a compound of formula I or a mixture of such compounds are the subject of the invention. Such vehicle paints are known.

All types used in industrial painting, preferably stove enamels, are suitable as paints. The latter are preferably "baked" at over 100 ° C to obtain optimal properties. In particular, in combination with the light stabilizers mentioned, lacquers (so-called wet lacquers) which contain as binders are preferred: combinations of oil-modified polyester resins (oil alkyd resins) and melamine-formaldehyde resins or combinations of crosslinking polyacrylate resins and melamine-formaldehyde resins or combinations of saturated polyesters and melamine-formaldehyde resins or self-crosslinking polyacrylate resins or also poly-acrylate resins with copolymerized styrene. Furthermore, two-component acrylate resin lacquers consisting of hydroxyl-containing acrylate resin and aliphatic or aromatic isocyanates are also suitable, as are thermoplastic polyacrylate resin lacquers. Also worth mentioning are two-component polyurethane resin paints consisting of polyester resins containing hydroxyl groups and / or polyether resins, hardened with aliphatic or aromatic isocyanates. Thermoplastic polyacrylate resins or externally crosslinking polyacrylate resins in combination with melamine resins etherified with butanol, as well as polyacrylate resins containing hydroxy groups, hardened with aliphatic isocyanates, are of particular importance for metallisé paints. Also known are the powder coatings known per se, which e.g. were treated with a solution of compound (I).

Foreign crosslinking polyacrylate resins are e.g. B. described in H. Kittel, textbook of paints and coatings, Berlin, Vol. I, Part 2, page 712 or also in US-P 3,062,763.

The compound of the formula I can be added to the lacquer in any stage of lacquer production, in solid or dissolved form. The compound of the formula I is advantageously used in dissolved form in a suitable solvent in a highly concentrated form. By adding amounts of 0.02-5% UV stabilizer, mainly 0.2-2% according to formula I to the lacquers, the light and weather fastness of organic pigments in such stoving lacquers can be significantly increased, the tendency for hairline cracks to form in two layers. Coatings during weathering are significantly reduced and gloss retention improved significantly.

Surprisingly, this is also evident, in particular, in the case of metallisé paintwork, and an excellent long-term stabilization of the clearcoat film of two-layer metal-lisé paintwork with regard to hairline cracking and gloss retention.

The stabilization of two-layer metallization paints, as is usually used in the automotive industry, can be carried out either by adding to the base coat and / or by adding to the clear coat. Adding it to the clear coat alone shows a significant improvement in weathering stability.

Metallisé coatings according to the invention can be produced in many colors and also in light pastel colors.

The following examples illustrate the invention.

example 1

A mixture of 1.6 parts of triacetonamine, 1.5 parts of 30% formaldehyde solution and 1.4 parts of acetone cyanohydrin are stirred at 50 ° C. for 3 hours. Then 3 parts of methanol are added and the mixture is cooled to 0 ° C.

The connection falls

.ch.

in the form of crystals with a melting point of 100-102 ° C

Example 2

71 parts of a 70% strength solution of glycolic acid nitrile are added dropwise to a solution of 91 parts of 4-hydroxy-2,2,6,6-tetra-methylpiperidine in 180 parts of ethanol at 70 ° C. in the course of one hour and another 12 hours at 70 ° C stirred.

Ethanol is distilled off in vacuo. The residue is mixed with 80 ° warm toluene. The toluene-soluble part is separated off. The compound is obtained by cooling

CH

H3c Œ3

as crystals with a melting point of 119-121 C.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

7

653 019

Example 3

a) 4 parts of compound IV are hydrogenated in the presence of 2 parts of ammonia in 50 parts of tetrahydrofuran with 1 part of 5% rhodium on aluminum oxide as a catalyst at 60 ° C. and 50 atm of hydrogen pressure for 5 hours. The solvent is then distilled off. Compound 1 of Table 1 is obtained as residue.

b) 1.3 parts of LiAlH4 dissolved in 10 parts of tetrahydrofuran are initially introduced, then a solution of 1.9 parts of compound III in 20 parts of tetrahydrofuran is carefully added dropwise at 20 ° C. (exothermic reaction). The mixture is then heated to reflux for a further 15 hours. Excess LiAlH4 is destroyed with ethyl acetate. 1.4 parts of water are added to the reaction mixture. The precipitate is filtered off and washed with tetrahydrofuran. The solvent is distilled off from the filtrate. The remaining oil is dissolved in ether and the solution is cooled to approx. -30 ° C.

The compound 1 in Table 1 crystallizes out with a melting point of 96-98 ° C.

Example 4

A mixture of 4 parts of compound No. 1 of Table 1, 2 parts of acetic anhydride and 30 parts of ether is stirred at about 25 ° C. for 24 hours. Then the reaction mixture is neutralized with dilute sodium hydroxide solution, cooled to 0 ° C. and suction filtered. The solid is dried in a drying cabinet at 60 ° C. and 20 torr and then purified by column chromatography on silica gel with ethanol / concentrated ammonia solution (100: 1). Compound No. 2 in Table 1 is thus obtained with a melting point of 138-140 ° C.

Example 5

A solution of 2.4 parts of compound no. 2 of Table 1 in 40 parts of tetrahydrofuran is added in portions at about 25 ° C. with 0.76 part of lithium aluminum hydride and stirred under reflux for 24 hours. After cooling to 10 ° C., 10 parts of water are slowly added dropwise and stirring is continued for half an hour. The resulting precipitate is filtered off and washed several times with tetrahydrofuran. Tetrahydrofuran is distilled off from the filtrate in vacuo, the residue no. 3 of Table 1 being obtained in the form of white crystals with a melting point of 135-136 ° C.

Example 6

2.2 parts of compound no. 1 in Table 1, 20 parts of diethyl ether and 10 parts of sodium hydroxide solution are placed in a separating funnel and 1.5 parts of benzoyl chloride are carefully added. A white solid is noticed, which is filtered off and washed with diethyl ether. After recrystallization from acetone, compound No. 4 in Table 1 is obtained in the form of white crystals with a melting point of 156-157 ° C.

Example 7

5.3 parts of compound no. 1, table 1,100 parts of ether, 15 parts of water and 27 parts in sodium hydroxide solution are combined and, with stirring, 3.2 parts of sebacic acid dichloride are added within 15 minutes, a white solid being formed. This is suction filtered and dried in a vacuum drying cabinet at approx. 60 ° C. Compound No. 5 in Table 1 is thus obtained as white crystals with a melting point of 193-196 C.

Example 8

5 parts of Compound No. 5 in Table 1 are refluxed in 100 parts of tetrahydrofuran with 2.7 parts of lithium aluminum hydride for 48 hours. After carefully adding 25 parts of water at approx. 0 C, the resulting suspension is filtered off with suction and washed several times with ether. The solvent is distilled off from the filtrate in vacuo. Recrystallization from acetone and subsequent column chromatography on silica gel with ethanol / concentrated ammonia solution (10: 1) gives compound No. 6 in Table 1 with a melting point of 162-163 X.

Example 9

A mixture of 50 parts of acetone, 3.7 parts of cyanuric chloride and 8 parts of compound no. 1, Table 1 is heated to 35 ° C. The solution of 1.6 parts of sodium hydroxide in 10 parts of water is added dropwise within 15 minutes and the reaction mixture was stirred for 6 hours at 35 ° C. The resulting mixture was then poured onto 200 parts of water, and the white solid which had precipitated was filtered off with suction, washed with water and recrystallized from acetone / water, giving compound No. 7 in the table 1 with a melting point of 190-193 C.

Example 10

A mixture of 4 parts of Compound No. 7, Table 1, 1.6 parts of Compound No. 1, Table 1, 0.3 part of powdered sodium hydroxide and 30 parts of toluene are refluxed for 23 hours. After cooling to 0 ° C., the precipitated solid is filtered off, washed several times with water and dried. Compound No. 8, Table 1 with a melting point of 198-200 ° C. is thus obtained.

Example 11

4.7 parts of 2,4-dichloro-6-piperidino-l, 3,5-triazine and 4 parts of Compound No. 1, Table 1, are dissolved in 30 parts of acetone and heated to 35-40 ° C. A solution of 0.8 part of sodium hydroxide in 5 parts of water is then added dropwise within 30 minutes and the mixture is stirred at 35 ° -10 ° C. for 5 hours. The reaction mixture is poured onto 200 parts of ice water. The precipitated white solid is filtered off, washed several times with water and dried over phosphorus pentoxide in a desiccator.

After recrystallization from acetone, compound No. 9, Table 1 with a melting point of 138-140 ° C.

In a manner analogous to Examples 9-11, compound No. 10 of Table 1 is prepared.

Example 12

1.4 parts of compound no. 3, Table 1, 1.7 parts of 2-chloro-4,6-bis-piperidino-l, 3,5-triazine, 0.25 part of powdered sodium hydroxide and 30 parts of toluene are added for 48 hours Reflux stirred. The reaction mixture is cooled and filtered. The solvent is distilled off from the filtrate in vacuo. The residue is column chromatographed on silica gel with ethyl acetate.

The purified product is recrystallized from ethyl acetate to give compound No. 11 in Table 1 with a melting point of 145-146 ° C.

Example 13

2.7 parts of compound no. 1 of the table 1.1.5 parts of triethylamine and 100 parts of toluene are stirred at 0 ° C. with a solution of 3.6 parts of 3- (4-hydroxy-3,5-di -tert.-butyl) phenylpropionyl chloride was added dropwise in 30 parts of toluene. After dropping, the Ge5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

653 019

8th

mixed for a further 24 hours at approx. The resulting white precipitate is filtered off, the solvent is distilled off in vacuo from the filtrate. After column chromatography on silica gel with toluene / acetone (1.1) and recrystallization from hexane, compound No. 12 in Table 1 is obtained.

Example 14

4 parts of compound no. 1 in Table 1, 5.8 parts of methyl 3- (4-hydroxy-3,5-di-tert-butyl) phenylpropionate and 0.2 part of sodium hydride are refluxed in 30 parts of xylene for 4 hours cooked. After cooling, the reaction mixture is filtered. The solvent is distilled off from the filtrate in vacuo. The residue is column chromatographed on silica gel with toluene / acetone (9: 1). After recrystallization from hexane, compound no. 13 of table 1 with a melting point of 95-97 "C.

Example 15

11.1 parts of 3- (4-hydroxy-3,5-di-tert-butyl) phenylpropionic acid, 8.2 parts of dicyclohexylcarbodiimide and 0.6 part of 4-pyrrolidinopyridine in 150 parts of chloroform are introduced. A solution of 4 parts of compound no. 1 Table 1 in 25 parts of chloroform is added dropwise at about 25 ° C. After stirring for 26 hours, the white solid which has precipitated is filtered off with suction, the solvent is distilled off from the filtrate and the residue which remains is column-chromatographed on silica gel using toluene / acetone (4: 1). After recrystallization from hexane, compound No. 14 in Table 1 is obtained with a melting point of 85-86 C.

Example 16

A mixture of 0.8 parts of compound no. 1 in table 1.3.7 parts of stearic acid chloride and 20 parts of toluene is boiled under reflux for 1 hour. After cooling down

15

20th

20 C excess acid chloride is reacted with methanol and the reaction mixture is adjusted to pH 10 with 2N sodium hydroxide solution. The precipitate is filtered off and washed with ether. The organic phase is separated from the filtrate, the aqueous phase is extracted with ether and the combined organic phases are dried with sodium sulfate. The solvent is distilled off and the remaining crystalline residue is column chromatographed over silica gel with ether / hexane (2: 1). Recrystallization from ethanol gives compound No. 15, Table 1 in the form of white crystals with a melting point of 77-79 ° C.

Example 17

A mixture of 1.1 parts of compound No. 6 in Table 1, 5 parts of stearic acid chloride and 40 parts of toluene is boiled under reflux for 22 hours. After cooling to 20 ° C., 2 parts of methanol are added and the mixture is neutralized with 2N sodium hydroxide solution. The solvent is distilled off from the organic phase. Recrystallization of the remaining crude product from acetone gives compound no. 17 of table 1 with a melting point of 38-40 ° C.

Example 18

1.7 parts of hexame-25-ethylene diisocyanate in 20 parts of ether are introduced under a nitrogen atmosphere and, with stirring at about 25 ° C., with a solution of 2 parts of compound no. 1, Table 1 in 30 parts of toluene / ether (1: 2) transferred. A white precipitate forms immediately. After stirring for 4 hours, the crystalline solid is suction filtered and washed with hexane.

Compound No. 16 in Table 1 is thus obtained, with a melting point of 58-62 ° C. After melting, the product solidifies again due to polymerization.

Table 1

? 2

* 3 - n-ch2 -

O-R,

a =

H

-N

- au -

h3c œ3

No.

R,

R2

r3

Mp ° C

h h h h

H

O n

-c-ch, h

O n

-C-Ph h h

-c2h5

H

96-98

138-140 135-136

156-157

O

O

h h h

h h h

-C-fCH ^ gC-A

^ 'Œ2 ^ 10 ~ A

N ^ N Cl N Cl

193-196 162-163

190-193

653 019

Table 1 (continued)

No.

R.

R2

R3

M.p. C

8 h

9 h

10 h

11 h

12 h

O

14

13 -c-fch where / -0h

2 2

do. O

15 - ^ - (ch23-16-ch3

H H H

-C2H5 H

H .

-c-fch

À

O

-ciœ2) -2 oh

H

O

II

-OH

"0 € CH2) I6CH3

H

H

198-200

138-140

178-180 145-146 70-72

95-97

85-86 77-79

16

17th

H

21 (

-C-NH (.CH2) 6N = C = 0 H

h3c ch3

Y- \ o n

t

LÇ o

CH2 Œ2 / ° ~ C ~ C17H35

C17K35

58-62

38-40

Example 19

0.5 pph of compound no. 15, table 1 are worked into a non-UV-stabilized polypropylene in a mixing kneader at 180 JC. A 3 mm thick plate is pressed from the plasticine. A 0.3 mm thick film is also produced. The film is exposed in the Atlas Weatherometer WRC 600 (xenon lamp) and the damage caused by the UV light is determined by the increase in the carbonyl band at 5.8 H using the compensation method. You get very good results compared to the sample without UV stabilizer.

According to the German DIN standard 53453, the change in impact strength is measured on punched lines of the 3 mm plate after exposure in the Atlas Weatherometer WRC 600. In comparison to the sample without UV stabilizer, very good results are obtained.

Example 20

Use in car topcoat.

Paint build-up

Structure of the two-layer Metallisé lacquer from an h3c .gi3

Base coat and a clear coat according to the following composition.

I. Base coat, consisting of (GT = parts by weight):

12.60 GT commercial polyacrylate resin, cross-linking (Viacryl SC 344, Vianova, Vienna) (delivery form 50% in xylene / butanol 4: 1) according to definition DIN 53'186 2.19 GT commercial butanol-etherified melamine resin, medium reactive, delivery form 72% in isobutanol (Maprenal MF 800, Casella) produced by poly-condensation from 1 mol melamine with 3-6 mol formaldehyde, etherified with 3-6 mol butanol according to definition DIN 53'187 0.96 GT butanol 0.26 GT colloidal silica 7 , 05 GT xylene

52.00 GT cellulose acetobutyrate solution, 20% (composition see below)

60

65

653 019

6.80 pbw aluminum paste, non-floating (non-leafing), commercial form 65% in alkyl glycol acetate according to definition DIN 55'923 18.14 pbw butyl acetate

Cellulose Acetobutyrate Solution 20.00 GT cellulose acetobutyrate

Acetyl content approx. 13.6%

Butyryl content 38.7%

Hydroxyl content 1.25%

Viscosity in poise (d Pa.s), 20% in acetone: 2.0 10.00 GT butanol 35.50 GT xylene 35.00 GT butyl acetate 100.00 GT

II. Clear coat (top coat)

consisting of

80.00 GT polyacrylate resin (analogous to base coat)

13.75 GT melamine resin (analogous to base coat)

4.50 pbw of butyl glycolic acid 7.50 pbw of solvent. Aromatic mixture boiling range approx. 186-212 C

6.00 GT solvent, aromatic mixture boiling range approx. 155-178 C.

Execution:

Paint build-up Base coat I additionally colored with 0.3 GT copper phthalocyanine blue C.I. Pigment Blue 15: 1, applied by spraying, layer thickness approx. 20 p. (without UV stabilizer).

Overpainted (spray application, after the base coat has dried)

a) with clear varnish according to II

b) with clear lacquer according to II additionally containing 1 part by weight of the compound from Example 2

a) and b) baked at 140 ° C for 30 minutes.

Weathered 1 year Florida, 5: southward inclination.

Sheets according to example b) achieve a significantly better rating than those according to example a).

10th

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

S

Claims (4)

653 019 PATENT CLAIMS 1. N-ß-Aminoethylpiperidine compounds of the formula R. - CH2 - CH2 - N H3C CH wherein R! Hydrogen or a radical 0 H X the direct bond. Oxygen or NH, R2 hydrogen or alkyl (C1 I8) or a radical (a), R3 hydrogen. Alkyl (CM8) or one of the radicals (b), (c) or (d): 2. A process for the preparation of compounds of For-45 mei I according to claim 1, characterized in that one mole of a compound of formula III or IV - (e). C ^ / H3 50 (CH3> 3C n zero, 1 or 2, ' R5 independently of one another chlorine, NC-CH2 - N V = Q (In> or ÇJ "N U3 \ / CT3 (f) r CR XH, 3 3 CH3 7CH3 60 or - N - Œ2- CK2 - N NC-CH, OHx (?) '65 fr (IV) ? 2 Rg - X - C - N CH "- H-C CH0 * 2 N - CH2 - CH2 - N, 15 - C - X - R4 (a) where m 2-10, H3C Cti3 à (C). o it c - x 0 3. A process for the preparation of compounds of the formula I according to claim 1, characterized in that one mole of a compound of the formula III or IV, according to claim 2, is reduced and with one or two moles of a compound of the formula R4-CO-OH or a functional derivative thereof, or with one or two moles of a compound of the formula R4-0-C0-Cl or R4-N = C = O acylated, where R4 has the meanings given in Claim 1. 3rd 653 019 3 CH. h3c œ3 reduced and reacted with one or two moles of a C [_18-alkylating agent. 3 yL. 3rd H3C ^ H3 - R -i (<*) R'2 is hydrogen or alkyl (CMg), where if R3 is one of the radicals (c) or (d), R2 = R'2, or R2 and R3 together with the N atom to which they are attached, a succinimide, maleimide or phthalide ring, R4 alkyl (C, _18) which is optionally substituted for -N = C = O by -N = C = O, cycloalkyl (C5_g), phenylalkyl (C! _4), optionally together with 1 or 2 alkyl (C, _12) at most 18 carbon atoms substituted phenyl, or (Œ3> 3 R6 is alkylene (C2_io) or phenylene which is optionally substituted by alkyl (C] _9} and for X = direct bond R6 is also —CH2— or the direct bond, R7 is hydrogen, alkyl (C] _18), ß-hydroxyethyl, 40 Rs alkyl (C, _18), ß-hydroxyethyl or phenyl, or R7 and Rs together with the N atom to which they are attached are a residue of the piperidine or morpholines. 4. A process for the preparation of compounds of the formula I according to claim 1, characterized in that one mole of a compound of the formula III or IV, according to claim 2, is reduced and with one mole of a compound of the formula Cl N oN R5 R!